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EP0410420A2 - Solid oxide fuel cell and method of manufacturing the same - Google Patents

Solid oxide fuel cell and method of manufacturing the same Download PDF

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Publication number
EP0410420A2
EP0410420A2 EP90114266A EP90114266A EP0410420A2 EP 0410420 A2 EP0410420 A2 EP 0410420A2 EP 90114266 A EP90114266 A EP 90114266A EP 90114266 A EP90114266 A EP 90114266A EP 0410420 A2 EP0410420 A2 EP 0410420A2
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EP
European Patent Office
Prior art keywords
electrolyte layer
fuel cell
solid oxide
oxide fuel
layer
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Granted
Application number
EP90114266A
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German (de)
French (fr)
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EP0410420A3 (en
EP0410420B1 (en
Inventor
Niroh Kitagawa
Masayuki Kitoh
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Taiheiyo Cement Corp
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Onoda Cement Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the present invention relates to a solid oxide fuel cell and a method of manufacturing the same.
  • a solid oxide fuel cell comprises, as shown in Fig. 1, a first region 8 filled with a fuel gas, a second region 9 filled with air or oxygen, and a solid oxide fuel cell unit 5 separating these regions.
  • a temperature e.g., 1000°C
  • electromotive force is generated between a fuel electrode layer 2 and an air electrode layer 4, both within the unit 5, whereby the cell generates electrical energy.
  • the electrolyte layer 3 is required to possess good oxygen ion conductivity, and gas stopping power which hardly permits gas to pass therethrough.
  • the gas stopping power is required from such an electrolyte layer because, if part of the fuel gas in the fuel gas region transmits through the electrolyte layer to reach the air or oxygen region, or conversely if part of the oxygen gas reaches the fuel gas region through the layer, there is the risk of a combustion reaction between the fuel gas and the oxygen gas. In such cases, part of the fuel gas will be consumed, becoming unable to participate in the generation of power. This leads to a drop in power generation efficiency.
  • Another problem is that the heat of combustion causes local heating of the cell, resulting in breakage of the unit, etc.
  • the electrolyte layer is formed by one of the following methods:
  • the known gaseous phase method is capable of obtaining an electrolyte layer having great gas stopping power
  • the speed at which the layer is formed is as low as to be about one hundredth (1/100) of that in the conventional spray coating method.
  • the zirconium chloride and the yttrium chloride are used as being mixed with helium gas, while the vapor used is mixed with hydrogen, the required running cost is high, and it is also necessary to assure safety.
  • the conventional spray coating method is capable of forming an electrolyte layer at high speed, the produced layer has insufficient gas stopping power.
  • the fuel cell units obtained may suffer from local heating due, for instance, to gas leakage, and end up with a short service life.
  • the second method also fails to be adequately usable in practice.
  • the gas stopping power questioned here is evaluated in terms of the gas permeability coefficient P (cm4/g ⁇ sec) by using a certain measuring device whose basic construction is shown in Fig. 2.
  • a predetermined pressure is applied to a pressurizing region 16 of the device. Then, the quantity Q of gas (cm3/sec) which reaches a discharge region 17 of the device after passing through an electrolyte layer 3 formed on a porous substrate 1 is measured by a gas flowmeter 14.
  • the quantity Q (cm3/sec) of the transmitted gas changes in inverse proportion to the thickness t (cm) of the electrolyte layer, and in direct proportion to both the difference Pd (g/cm2) in pressure between the pressurizing region 16 and the discharge region 17, and the area S (cm2) of the electrolyte layer.
  • the gas permeability coefficient P (cm4/g ⁇ sec) can be calculated from the following equation:
  • the electrolyte layer should have as small a gas permeability coefficient P as possible.
  • an electrolyte layer is formed on a substrate having a coefficient of thermal expansion substantially equal to that of the electrolyte layer by a plasma spray coating process, and is then subjected to heat treatment at a temperature above 1300°C for a predetermined period of time, it is possible to form an electrolyte layer having a gas permeability coefficient which is far smaller than that of an electrolyte layer formed by a method consisting of only a spray coating process.
  • the present invention is directed to the provision of a solid oxide fuel cell having a solid oxide fuel cell unit including such an electrolyte layer, and a method of manufacturing the electrolyte layer.
  • Plasma spray coating was effected to form an electrolyte layer of yttria-stabilized zirconia (yttria: 8 mol. %) on a porous substrate of calcia-stabilized zirconia (calcia: 10 mol. %).
  • the temperature of the formed electrolyte layer was raised to 1450°C at an increment rate of 50°C/hour. Then, the layer was maintained at that temperature for six hours. Thereafter, the temperature of the layer was lowered at a reduction rate of 50°C/hour.
  • a second electrolyte layer was obtained in exactly the same manner except that it was subjected to only the plasma spray coating.
  • the gas permeability coefficient of the first electrolyte layer which was subjected to both the plasma spray coating and the heat treatment, and that of the second electrolyte layer which was subjected to only the plasma spray coating were measured using nitrogen gas at 25°C.
  • the layer which was only plasma spray coated had a gas permeability coefficient of 3.0 x 10 ⁇ 6 cm4/g ⁇ sec
  • the layer which was plasma spray coated and then heat treated had a gas permeability coefficient of 0.6 x 10 ⁇ 6 cm4/g ⁇ sec.
  • the heat treatment enabled a five-to-one (1/5) reduction in the gas permeability coefficient.
  • the third electrolyte layer had a gas permeability coefficient which was at least ten times greater than that of the fourth electrolyte layer.
  • the reason for this fact was considered to be as follows: the thermal expansion coefficient (8 x 10-6) of the porous alumina substrate was so different from the thermal expansion coefficient (10 x 10 ⁇ 6) of the third electrolyte layer of yttria-stabilized zirconia that cracks were formed in the electrolyte layer which was thinner than the substrate.
  • the formation of cracks in the electrolyte layer was confirmed by microphotography using an electron microscope.
  • the used substrate is a substrate made of a calcia-­stabilized zirconia material having a thermal expansion coefficient that is of the order of 9.7 x 10 ⁇ 6 and is thus substantially equal to that of the electrolyte layer to be formed, it is possible, by suitable heat treatment, to greatly reduce the gas permeability coefficient of the resultant electrolyte layer.
  • the heat treatment temperature can be below 1300°C. However, if the temperature is, for instance, about 1250°C, the required heat treatment period is about 100 hours, and is thus considerably long. The required heat treatment period can be curtailed with increases in the heat treatment temperature. If the heat treatment temperature is 1600°C, the required heat treatment period is about 1 hour.
  • the present invention makes it possible to advantageously combine a spray coating process, which is capable of layer formation at very high speeds, with a large heat treatment apparatus, which is already employed in industrial use to effect a continuous process, in order to form an electrolyte layer having great gas stopping power at low cost and with a simple apparatus.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

Disclosed are a solid oxide fuel cell and a method of manufacturing the same. An electrolyte layer (3) of the solid oxide fuel cell unit (5) is formed by spray coating the layer on a substrate (1) having a coefficient of thermal expansion which is substantially equal to that of the electrolyte layer (3), and the formed layer is then subjected to heat treatment.

Description

    BACKGROUND OF THE INVENTION Field of the Invention
  • The present invention relates to a solid oxide fuel cell and a method of manufacturing the same.
    • Description of the Related Art
  • A solid oxide fuel cell comprises, as shown in Fig. 1, a first region 8 filled with a fuel gas, a second region 9 filled with air or oxygen, and a solid oxide fuel cell unit 5 separating these regions. When the unit 5 and the gases in the regions 8 and 9 are heated to a temperature, e.g., 1000°C, above which ionic conduction by oxygen occurs in an electrolyte layer 3 of the unit 5, electromotive force is generated between a fuel electrode layer 2 and an air electrode layer 4, both within the unit 5, whereby the cell generates electrical energy. The electrolyte layer 3 is required to possess good oxygen ion conductivity, and gas stopping power which hardly permits gas to pass therethrough.
  • The gas stopping power is required from such an electrolyte layer because, if part of the fuel gas in the fuel gas region transmits through the electrolyte layer to reach the air or oxygen region, or conversely if part of the oxygen gas reaches the fuel gas region through the layer, there is the risk of a combustion reaction between the fuel gas and the oxygen gas. In such cases, part of the fuel gas will be consumed, becoming unable to participate in the generation of power. This leads to a drop in power generation efficiency.
  • Another problem is that the heat of combustion causes local heating of the cell, resulting in breakage of the unit, etc.
  • The electrolyte layer is formed by one of the following methods:
    • ① A method (CVD-EVD method) in which zirconium chloride and yttrium chloride are transformed into their gaseous state at a high temperature and under a reduced pressure, the gases reacting with water vapor to deposit an electrolyte layer. This method will hereinafter be referred to as "the gaseous phase method".
    • ② A method in which an electrolyte powder is spray coated to form an electrolyte layer. This method will hereinafter be referred to as "the conventional spray coating method".
  • Although the known gaseous phase method is capable of obtaining an electrolyte layer having great gas stopping power, the speed at which the layer is formed is as low as to be about one hundredth (1/100) of that in the conventional spray coating method. Furthermore, the first method requires strict reaction conditions consisting of a temperature ranging from 1100 to 1200°C, and a degree of vacuum of about 1 Torr (1 Torr = 1 mmHg), hence, it requires a large apparatus. Still further, since the zirconium chloride and the yttrium chloride are used as being mixed with helium gas, while the vapor used is mixed with hydrogen, the required running cost is high, and it is also necessary to assure safety.
  • Another drawback of the gaseous phase method is that since it involves a process performed under reduced pressure, the apparatus used cannot be an apparatus for continuous production but only an apparatus for batch production. Because production by a batch type apparatus requires a long time to raise or lower the temperature, the production efficiency is low. As a result, the fuel cell units obtained are extremely expensive. Thus, the first method is only scarcely suitable for practical use.
  • Although the conventional spray coating method is capable of forming an electrolyte layer at high speed, the produced layer has insufficient gas stopping power. As a result, the fuel cell units obtained may suffer from local heating due, for instance, to gas leakage, and end up with a short service life. Thus, the second method also fails to be adequately usable in practice.
  • The gas stopping power questioned here is evaluated in terms of the gas permeability coefficient P (cm⁴/g · sec) by using a certain measuring device whose basic construction is shown in Fig. 2.
  • First, a predetermined pressure is applied to a pressurizing region 16 of the device. Then, the quantity Q of gas (cm³/sec) which reaches a discharge region 17 of the device after passing through an electrolyte layer 3 formed on a porous substrate 1 is measured by a gas flowmeter 14.
  • When the type as well as the temperature of the gas are fixed, the quantity Q (cm³/sec) of the transmitted gas changes in inverse proportion to the thickness t (cm) of the electrolyte layer, and in direct proportion to both the difference Pd (g/cm2) in pressure between the pressurizing region 16 and the discharge region 17, and the area S (cm²) of the electrolyte layer. On the basis of these facts, the gas permeability coefficient P (cm⁴/g · sec) can be calculated from the following equation:
    Figure imgb0001
     The electrolyte layer should have as small a gas permeability coefficient P as possible.
    • SUMMARY OF THE INVENTION
  • If an electrolyte layer is formed on a substrate having a coefficient of thermal expansion substantially equal to that of the electrolyte layer by a plasma spray coating process, and is then subjected to heat treatment at a temperature above 1300°C for a predetermined period of time, it is possible to form an electrolyte layer having a gas permeability coefficient which is far smaller than that of an electrolyte layer formed by a method consisting of only a spray coating process. The present invention is directed to the provision of a solid oxide fuel cell having a solid oxide fuel cell unit including such an electrolyte layer, and a method of manufacturing the electrolyte layer.
    • BRIEF DESCRIPTION OF THE DRAWINGS
    • Fig. 1 is a schematic drawing of the structure of a solid oxide fuel cell; and
    • Fig. 2 is a schematic drawing of the structure of a device for measuring the gas permeability coefficient of an electrolyte layer.
    DESCRIPTION OF THE PREFERRED EMBODIMENTS.
  • The present invention will now be described by way of examples.
    • Example 1
  • Plasma spray coating was effected to form an electrolyte layer of yttria-stabilized zirconia (yttria: 8 mol. %) on a porous substrate of calcia-stabilized zirconia (calcia: 10 mol. %). The temperature of the formed electrolyte layer was raised to 1450°C at an increment rate of 50°C/hour. Then, the layer was maintained at that temperature for six hours. Thereafter, the temperature of the layer was lowered at a reduction rate of 50°C/hour.
  • A second electrolyte layer was obtained in exactly the same manner except that it was subjected to only the plasma spray coating.
  • The gas permeability coefficient of the first electrolyte layer which was subjected to both the plasma spray coating and the heat treatment, and that of the second electrolyte layer which was subjected to only the plasma spray coating were measured using nitrogen gas at 25°C. As a result, the layer which was only plasma spray coated had a gas permeability coefficient of 3.0 x 10⁻⁶ cm4/g · sec, whereas the layer which was plasma spray coated and then heat treated had a gas permeability coefficient of 0.6 x 10⁻⁶ cm⁴/g · sec. Thus, it was found that the heat treatment enabled a five-to-one (1/5) reduction in the gas permeability coefficient.
    • Example 2
  • A third electrolyte layer, which was plasma spray coated and then heat treated, as well as a fourth electrolyte layer, which was only plasma spray coated, were obtained under exactly the same conditions as in Example 1 except that porous alumina substrates were used. When their gas permeability coefficients were measured, the third electrolyte layer had a gas permeability coefficient which was at least ten times greater than that of the fourth electrolyte layer. The reason for this fact was considered to be as follows: the thermal expansion coefficient (8 x 10-6) of the porous alumina substrate was so different from the thermal expansion coefficient (10 x 10⁻⁶) of the third electrolyte layer of yttria-stabilized zirconia that cracks were formed in the electrolyte layer which was thinner than the substrate. In fact, the formation of cracks in the electrolyte layer was confirmed by microphotography using an electron microscope.
  • From the results of Examples 1 and 2, it can be said that if the used substrate is a substrate made of a calcia-­stabilized zirconia material having a thermal expansion coefficient that is of the order of 9.7 x 10⁻⁶ and is thus substantially equal to that of the electrolyte layer to be formed, it is possible, by suitable heat treatment, to greatly reduce the gas permeability coefficient of the resultant electrolyte layer.
  • The heat treatment temperature can be below 1300°C. However, if the temperature is, for instance, about 1250°C, the required heat treatment period is about 100 hours, and is thus considerably long. The required heat treatment period can be curtailed with increases in the heat treatment temperature. If the heat treatment temperature is 1600°C, the required heat treatment period is about 1 hour.
  • The present invention makes it possible to advantageously combine a spray coating process, which is capable of layer formation at very high speeds, with a large heat treatment apparatus, which is already employed in industrial use to effect a continuous process, in order to form an electrolyte layer having great gas stopping power at low cost and with a simple apparatus.
  • While the present invention has been described in its preferred embodiments, it is to be understood that the invention is not limited thereto but may be practiced as modified or varied without departing from the scope of the invention which is defined by the appended claims.

Claims (7)

1. A solid oxide fuel cell comprising:
a solid oxide fuel cell unit (5) consisting of a fuel electrode layer (2), an electrolyte layer (3) and an air electrode layer (4), said layers (2, 3, 4) being subsequently superimposed to form an integral unit on a substrate (1);
a first region (9) filled with air or oxygen; and
a second region (8) filled with a fuel gas, said first and second regions (9, 8) being positioned as separated from each other by said fuel cell unit (5),
said solid oxide fuel cell being characterised in that said substrate (1) has a coefficient of thermal expansion which is substantially equal to that of said electrolyte layer (3), and said electrolyte layer is obtained by effecting spray coating to form said electrolyte layer (3) and subjecting the formed layer to heat treatment.
2. A solid oxide fuel cell according to claim 1, wherein said electrolyte layer (3) is made of yttria-­stabilized zirconia, and said substrate is made of yttria-­stabilized zirconia.
3. A solid oxide fuel cell according to claim 1, wherein said electrolyte layer (3) is made of yttria-­stabilized zirconia, and said substrate is made of calcia-­stabilized zirconia.
4. A solid oxide fuel cell according to claim 1, wherein said electrolyte layer (3) is made of yttria-­stabilized zirconia, and said substrate is made of magnesia-­stabilized zirconia.
5. A method of manufacturing a solid oxide fuel cell adapted to prepare a solid oxide fuel cell unit (5) consisting of a fuel electrode layer (2), an electrolyte layer (3) and an air electrode layer (4), said layers (2, 3, 4) being subsequently superimposed to form an integral unit on a substrate (1), and prepare a first region (9) filled with air or oxygen as well as a second region (8) filled with a fuel gas, said regions being positioned as separated from each other by said unit,
said method being characterised by the steps of:
preparing a substrate (1) having a coefficient of thermal expansion which is substantially equal to that of an electrolyte layer (3) to be formed thereon; and
obtaining said electrolyte layer (3) by effecting spray coating to form said electrolyte layer (3) and subjecting the formed layer to heat treatment.
6. A method according to claim 5, wherein said heat treatment is effected at a temperature above 1300°C.
7. A method according to claim 5, wherein said heat treatment is effected for a period of time at least equal to 1 hour.
EP90114266A 1989-07-28 1990-07-25 Solid oxide fuel cell and method of manufacturing the same Expired - Lifetime EP0410420B1 (en)

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JP196324/89 1989-07-28
JP1196324A JPH0362459A (en) 1989-07-28 1989-07-28 Solid electrolyte fuel cell and its preparation

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EP0410420A2 true EP0410420A2 (en) 1991-01-30
EP0410420A3 EP0410420A3 (en) 1991-10-09
EP0410420B1 EP0410420B1 (en) 1994-03-16

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476808A1 (en) * 1990-09-04 1992-03-25 Ngk Insulators, Ltd. Process for producing a composite body and use in a solid oxide fuel cell
EP0507520A2 (en) * 1991-03-28 1992-10-07 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film
EP0524013A1 (en) * 1991-07-19 1993-01-20 Ngk Insulators, Ltd. Solid electrolyte type fuel cell and method for producing the same
EP0552055A2 (en) * 1992-01-17 1993-07-21 Ngk Insulators, Ltd. A process for producing solid oxide fuel cells
US5527633A (en) * 1992-09-17 1996-06-18 Ngk Insulators, Ltd. Solid oxide fuel cells, a process for producing solid electrolyte films and a process for producing solid oxide fuel cells

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US5162167A (en) * 1990-09-11 1992-11-10 Allied-Signal Inc. Apparatus and method of fabricating a monolithic solid oxide fuel cell
GB9023091D0 (en) * 1990-10-24 1990-12-05 Ici Plc Composite membranes and electrochemical cells containing them
JPH05135787A (en) * 1991-03-28 1993-06-01 Ngk Insulators Ltd Manufacture of solid electrolyte film and manufacture of solid electrolyte fuel cell
JP2970186B2 (en) * 1992-03-17 1999-11-02 松下電器産業株式会社 Manufacturing method of alkaline battery
JPH06103990A (en) * 1992-09-18 1994-04-15 Ngk Insulators Ltd Solid electrolytic type fuel cell and manufacture thereof
US5391440A (en) * 1994-02-14 1995-02-21 Westinghouse Electric Corporation Method of forming a leak proof plasma sprayed interconnection layer on an electrode of an electrochemical cell
US5389456A (en) * 1994-02-14 1995-02-14 Westinghouse Electric Corporation Method and closing pores in a thermally sprayed doped lanthanum chromite interconnection layer
US5426003A (en) * 1994-02-14 1995-06-20 Westinghouse Electric Corporation Method of forming a plasma sprayed interconnection layer on an electrode of an electrochemical cell
DE102004044597B3 (en) * 2004-09-13 2006-02-02 Forschungszentrum Jülich GmbH Method for producing thin, dense ceramic layers
US11404710B2 (en) 2018-12-17 2022-08-02 Cummins Enterprise Llc Assembled portion of a solid oxide fuel cell and methods for inspecting the same

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476808A1 (en) * 1990-09-04 1992-03-25 Ngk Insulators, Ltd. Process for producing a composite body and use in a solid oxide fuel cell
US5234722A (en) * 1990-09-04 1993-08-10 Ngk Insulators, Ltd. Solid electrolyte film, solid oxide fuel cell comprising such a solid electrolyte film, and processes for producing such film and solid oxide fuel cell
EP0507520A2 (en) * 1991-03-28 1992-10-07 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film
EP0507520A3 (en) * 1991-03-28 1993-10-13 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film
US5418081A (en) * 1991-03-28 1995-05-23 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film for interconnectors of solid oxide fuel cells
EP0524013A1 (en) * 1991-07-19 1993-01-20 Ngk Insulators, Ltd. Solid electrolyte type fuel cell and method for producing the same
US5342703A (en) * 1991-07-19 1994-08-30 Ngk Insulators, Ltd. Solid electrolyte type fuel cell and method for producing the same
EP0552055A2 (en) * 1992-01-17 1993-07-21 Ngk Insulators, Ltd. A process for producing solid oxide fuel cells
EP0552055A3 (en) * 1992-01-17 1993-07-28 Ngk Insulators, Ltd. A process for producing solid oxide fuel cells
US5281490A (en) * 1992-01-17 1994-01-25 Ngk Insulators, Ltd. Process for producing solid oxide fuel cells
US5527633A (en) * 1992-09-17 1996-06-18 Ngk Insulators, Ltd. Solid oxide fuel cells, a process for producing solid electrolyte films and a process for producing solid oxide fuel cells

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EP0410420A3 (en) 1991-10-09
EP0410420B1 (en) 1994-03-16
US5051321A (en) 1991-09-24
JPH0362459A (en) 1991-03-18
DE69007361T2 (en) 1994-06-23
DE69007361D1 (en) 1994-04-21

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